Sulphide plastic and process of making same



Patented July 3, 1934 I v I 1 UNITED. STATES PATENT OFFICE I e 1.964.725 suhrnms ms'rrc AND mtooass or MAKING SAME col-moo nun, Montclalr, N. .r.,' asaignor to Ellis- Foster Company, a corporation of New Jersey No Drawing. Application July 31. 1929,

- Serial No. 382,597

Claims. (Cl. 260-8) v -This invention relates to a plastic product obor catalytic action, but appears also to orient tained by reaction betweenpolysulphides, and a' or determine the course of the reaction, at least mixture of aldehydes,-particularly formaldehyde to a' limited degree, and I therefore look upon and acetaldehyde or substances of an equivalent the alcohol as both an accelerating and orienting I character capable of forming a mixture of oragent. Since the alcohol is not appreciably .conon ganic sulphides of an amorphous plastic nature. verted by the action of the alkaline sulphide, it The invention will be illustrated by the reacmay be recovered at the close of the operation of tion of a mixture of formaldehyde and acetaldeforming the organic sulphide complex and may hyde with sodium'polysulphide, but it is underbe reused. a 10 stood that any other suitable sulphiding agent In some cases I may take the alcohol-contain- 5 may be employed, Preferably the reaction is caring spent liquor from the reaction and fortify it ried out by simultaneously reacting on the two with additional sulphur and/or sodium hyaldehydes or plurality of aldehydes with the suldroxide, as the case may be, and use it again phiding agent, but in certain cases I may react to bring about the conversion of additional quanll on the aldehydes successively or in any other titles of the aldehyde mixture. 7 desired way. There-also exists the step 01' form- One applicationof the present invention is ingthe plastic bodies separately by reacting on in forming resins or plastic bodies from the each aldehyde alone with the sulphiding agent products of oxidation [of petroleum. When and subsequently incorporating the product of petroleum hydrocarbons are oxidized in vapor these separately conducted reactions, employing phase by passingover a catalyst in the presence if necessary heating to intermingle, blend or reof air while proper conditions of temperature act the substances so prepared. regulation and the'like are maintained, a mix- When acetaldehyde is treated with sodium yture of aldehydes and alcohols can be obtained droxide solution or other fixed alkali it tends to which is well suited for treatment with a sulg5 resinify to form what is called acetaldehyde resin phjding e t; Natural gas and also gases from or aldehyde resin. It is possible in connection petroleum tills, including'cracking stills, may be with the procedur u i n a n ra W submitted to partial oxidation to make intermeabove to produce more or less acetaldehyde resin diate e i -in luding mixed aldehydes and but in the pr e of a u p n ag nt. such alcohols, thereby securing an alcoholic medium 30 as sodium poly ph calcium p ll well suited for conduct of the reaction and at the reaction also may be caused to produce ort same t yieldlnga mixture of t or m ganic sulphid bodies to a v considerable aldehydes which on being converted into sultent. By co-reaction of the plurality of aldephured products are particularly amorphous hydes I seek to obtain to a greater or lesser ex- Owing to their complexity In like manner aldeu ten interleaction and Productmn 0f afnmphmls hydes obtained by oxidation of heavy oils by air plastic bodies ranging from hard or brittle plasblowing under high pressure may b converted ties o those of a more rubbery and Yielding into plastic resinous bodies by the sulphide treatture. ment. The invention, therefore, includes the While acetaldehyde is set forth as a typical process of making plastic containing sulphur 4 aldehyde employ i formajldehyde P in combination comprising reacting on the mixed duce th duplex .OIganlC sulphid I also aldehydes of petroleum oxidation with an alkaif desired, use other aldehydes such as propyl alline polysmphide, referably in t presence of 'dehyde, butyl aldehyde, furfural, benzaldehyd an alcohol which preferably is one formed by cinnammic aldehyde and other saturated said oxidation process and the products of such 46 and .unsattlra'ted aldehydes of the Fatty or sulphide treatment, including alkali-polysulphatic series, the aromatic or cyclic series and phideqesimfled products of petroleum hydmmp the ancycnc series or heterocyclic series bon oxidation including the gases from petro- The reaction of mlxture of the lowex alde' leuni as well as the liquid products thereof.

des referabl is carried out in the presence of cons derable proportion of an alcoholic me- React-{19x1 may take place at atmwmisnc dium, such as methyl or ethyl alcohol ordinarily Sure m some cases Pressure V6559 may 1 5 diluted with water. In the presence of an alcoused to allow r operahon a rm spheric 1101 such as methanol in substantial proportion ssu s. So e o t e higher dehydes not an acceleration of the reaction takes place when readily 1: 1am; 1518.123 treated at Pressures low t h as sodium 01 sulphide is ema mosp eric es gl y zg rh e lcohol not only h s an accelerating. The cheapest iorm of polysulphide is that made from calcium oxide or hydroxide and sulphur, but calcium polysulphide may leave in the composition some residues of calcium which may not be suitable for the purpose intended and therefore sodium polysulphide is recommended for general purposes. It may be made from sulphur and sodium'hydroxide, carbonate, andthe like, either by wet or dry methods. Potassium polysulphide is more costly and ammonium polysulphide is not as suitable in many cases, but the use of these sulphiding agents is not precluded.

When it is desirable to separate acetaldehyde from formaldehyde in the form of resinous bodies, the mixture of the two aldehydes may be treated first with a small proportion of caustic soda to resinify the acetaldehyde or convert it to a non-volatile form (aldol, etc.) and separate such products of alkali conversion, then add sodium polysulphide and convert the formaldehyde to methylene sulphide or kindred olefin sulphide. Finally alcohol, if present, is then recovered. This procedure may be applied to the products of oxidation of natural gas containing formaldehyde, acetaldehyde, methyl alcohol, a small proportion of ethyl alcohol, water and certain substances in small proportion which polymerize very readily. Formaldehyde from this source is rather difficult to purify from the traces of higher aldehydes present and the treatment with the alkaline polysulphide converts the aldehydic content into plastic bodies, theamorphous character of which will be influenced by any higher aldehydes present. As an illustration of an aldehydic raw material mixture obtainedfrom the oxidation of the hydrocarbons of natural gas the following is perhaps typical of one rich is aldehydes; namely, 45 per cent formaldehyde, 12 to 15 per cent of acetaldehyde, 30 to 35 per cent of methyl alcohol, together with water approximately 10 per cent, ethyl alcohol one-half per cent: higher aldehydes and polymerizable bodies also present.

Still another procedure is that of reacting on a mixture of symmetrical ethylene dichloride and formaldehyde with alkaline polysulphide or similar sulphiding agent. The proportions of the aldehyde to'the dichloride may be varied over a considerable range, say from' one part of formaldehyde to 10 parts of ethylene dichloride on the one hand, and 10 parts of formaldehyde to one part of ethylene dichloride on the other hand. Acetaldehyde may be used in place of the formaldehyde in whole or in part. I

From the foregoing it will be-evident that the process thus may be employed to separate alcohols from aldehydes, converting the latter intonon-volatile products by a sulphiding reaction and separating the alcohol therefrom.

The following illustrate various phases of the invention, the proportions being given in parts by weight:

1. Sodium hydroxide 60, sulphur 96, water 100, methanol 50, acetaldehyde 25, formaldehyde 100. The sodium hydroxide and sulphur were heated under reflux condenser with the amount of water stated, forming the polysulphide, methanol and the aldehydes then added. Reaction took place forming a yellowish gummy mass soft to the touch but not sticky, resembling taily in the manner in which it can be pulled. The washed and dried product is substantially transparent and when drawn into strings shows a slight measure of elasticity or tendency to contract.

If formaldehyde is treated in the absence of acetaldehyde under like conditions a much harder product results.

hard mass .was obtained which softens in hot water and then can be washed in cooler water. This formaldehyde sulphide was incorporated with the acetaldehyde resin obtained as noted, using proportions of equal parts, 3 parts of formaldehyde sulphide to 1 part of the acetaldehyde product, and 10 parts of the formaldehyde sulphide to 1 part of said acetaldehyde product. While the resulting resins did not appear to have quite the same properties as those evidenced when the two aldehydes were reacted together, nevertheless the softening or fiuxing action of the'acetaldehyde resin was manifest. The product made with equal parts was soft and easily indented with the finger nail but was more opaque than the product made by coreaction of the two aldehydes. The compositions prepared with higher proportions of the formaldehyde sulphide were harder in proportion to theamount of the formaldehyde sulphide present.

3. The resinous composition described under Example 1 was incorporated with crepe rubber and on heating hardening resulted. The proportions used were crepe rubber 4 and acetaldehyde formaldehyde sulphur resin 1. Prior to the heating the composition gave a soft rubbery elastic mass.

4. Sodium hydroxide 60, sulphur 96, water 100, methanol 50, symmetricalethylene dichloride 25,

. formaldehyde 75.. a

The sodium hydroxide was dissolved in water, sulphuradded and the solution heated under a reflux condenser until thesulphur had dissolved,

the solution of sodium polysulphide which resulted being then cooled and methanol added together with the ethylene dichloride and formaldehyde. The mixture was heated for several hours on the water bath to 80 C. and then allowed to cool gradually by standing overnight. A soft resinous plastic results which pulls like taffy when washed under cold water. Product has strong coherence and may be drawn into threads or sheets by mere extension of a mass of the material.

5. Mixed aldehydes of petroleum origin. A mixture obtained by air-oxidation of natural gas was used containing approximately 27 per cent formaldehyde, 3 per cent acetaldehyde, and a considerable proportion of methanol, together with small quantities of higher aldehydes and acrid odies.

Sodium hydoxide 40, sulphur 96, water 150, the

- then allowed to stand over night and on examination of the cold solution it was found that a heavy, soft, plastic, coherent precipitate had formed constituting a yellowish emulsion. When heated to expel water there was obtained a clear, soft, brownish resin.

In using the mixed aldehydes as above the precipitate of plastic material is not always obtained, as will be illustrated by the following:

6. Sodium hydroxide 60, sulphur 96, water 150, mixed aldehydes as in Example 5, 150. Heated on water bath at 80-90" C. for 6 hours did not give any precipitate. The presence of some bodies in this crude aldehydic mixture evidently influences or hinders the formation of the plastic sulphide.

What I claim is:

1. The process of making a plastic containing sulphur in combination which comprises reacting on a mixture of formaldehyde and acetaldehyde with an alkaline polysulphide.

2. The process of making a plastic containing sulphur in combination which comprises reacting on a mixture of formaldehyde and acetaldehyde with an alkaline polysulphide in the presence of a lower aliphatic alcohol. 3. The process of making a plastic containing sulphur in combination which comprises reacting on a mixture of formaldehyde and acetaldehyde with an alkaline polysulphide in the presence of methanol.

4. The process of making a plastic containing sulphur in combination which comprises reacting on formaldehyde and a higher aldehyde with alkaline polysulphide.

5. The process of making a plastic containing sulphur in combination which comprises reacting on a mixture of aldehydes with alkaline polysulphide.

6. The process of making a plastic containing sulphur in combination which comprises reacting on the mixed aldehydes of petroleum oxidation with an alkaline polysulphide.

7. The process of making a plastic containing sulphur in combination which comprises reacting on the mixed aldehydes of petroleum oxidation with an alkaline polysulphide in the presence of an alcohol.

8. The process of separating alcohols from aldehydes in the composite product of petroleum oxidation which comprises reacting upon said composite product with alkaline polysulphide to convert the aldehydes into non-volatile products and separating the alcohol therefrom.

9. As a plastic, the co-reacted sulphur-containing reaction products of alkaline polysulphide on a mixture of formaldehyde and acetaldehyde.

10. Alkali-polysulphide-resinified products of petroleum oxidation products containing a plurality of aldehydes.

CARLETON ELLIS. 

